Chemo‐ and Stereoselective Iron‐Catalyzed Hydrosilylation of Ketones

The reduction of ketones with polymethylhydrosiloxane (PMHS) gives the corresponding alcohols in good to excellent yield applying iron‐based catalyst systems. In the case of prochiral ketones, the use of Fe(OAc)₂/(S,S)‐Me‐DuPhos leads to high enantioselectivity up to 99 % ee. The reaction proceeds in the presence of several functional groups such as esters, halides as well as conjugated double bonds, with high chemoselectivity. The advantage of this protocol is that the reaction requires no activating agents or additives.     

Harmonization of methods for analysis of cholesterol oxides in foods--the first portion of a long road toward standardization: interlaboratory study

A compilation of literature data on the content of cholesterol oxidation products (COP) in various food products and in blood demonstrates a large variation in content in products or tissues of very similar nature when analyzed in different laboratories according to a large number of methods. The lack of validated, internationally recognized methodology with published accuracy and precision has so far hindered such assessments. Hence an interlaboratory comparision of methodologies of COP analysis was undertaken on egg yolk powders (EYP), whole milk powders (WMP), skim milk powders (SMP), and lard (L). Each product type had one fresh sample (low) and one aged (high) in COP contents. A total of 17 sets of results on WMP, 15 on SMP and EYP, and 13 on L were compared. Overall results (mg/kg sample) varied extensively: Fresh EYP 0.72-265, aged EYP 2.51-361; fresh WMP 0.02-18.1, aged WMP 0.02-26.9; fresh SMP 0.02-6.51, aged SMP <0.01-6.51; fresh L 0.18-97, aged L 4.15-452. Some results were questioned, viz., those from laboratories not indicating substantial differences between samples "low" and "high" in total COP. Others were excluded because of lack of verification of identity of gas chromatographic peaks by mass spectrometry. Then a more narrow range of core results (mg/kg sample) was observed: Fresh EYP 5.69-29.5 sample, aged EYP 11.8-79.0; fresh WMP 0.12-1.76, aged WMP 1.17-13.7; fresh SMP <0.30-<1.21, aged SMP 0.30-2.26; fresh L 0.18-5.07, aged L 94.4-231. At a workshop discussing the results, numerous recommendations were made toward more reliable methodology for determination of COP in foods.     

Docking of Atomic Clusters Through Nonlinear Optimization

The problem of molecular docking is defined as that of finding a minimum energy configuration of a pair of molecular structures (usually consisting of proteins, DNA or RNA fragments). It is often assumed that the two interacting structures can be considered as rigid bodies and that it is of interest to researchers to develop methods which enable to discover the potential binding sites. Many different models have been proposed in the literature for the definition of the potential energy between two molecular structures, most of which contain at least a term (known as Van Der Waals interaction) which accounts for pairwise attraction between atoms, a repulsion term and a term which takes into account electrostatic forces (Coulomb interaction). Some well known models, and in particular those used in rigid docking, are based on the assumption that the only terms which are relevant in the process of docking are pairwise interactions between atoms belonging to the two different parts of the structure. In this paper the problem of finding the lowest energy configuration of a pair of biomolecular structures, considered as rigid bodies, is defined and formulated as a global optimization problem. In terms of dimension of the search space this formulation is not 'high-dimensional', as there are only six degrees of freedom: 3 translation and 3 rotation parameters. However the energy surface of the docking problem is characterized by a huge number of local minima; moreover each function evaluation is quite expensive (interesting structures usually possess a few thousand atoms each). So there is a strong need both of local and of global optimization procedures. In this paper a local optimization technique, based upon standard non linear programming software and a penalized objective function, is introduced and its potential usefulness in the context of global optimization is outlined.     

各向异性超常材料的偏振分离特性

提出了一种利用含有负介电常量和磁导率张量的各向异性超常材料实现偏振分离的方法。通过分析电磁波在无损耗各向异性超常材料中的传输性质以及透射率与入射角度的关系,分类比较了由不同符号的介电常量和磁导率张量组合而成具有不同波矢面的各向异性超常材料的偏振分离特性,比较结果表明波矢面为单叶双曲面和椭球双叶双曲面的各向异性超常材料的偏振分离特性强。前者可以实现入射波中的s分量和p分量中某一分量正折射,另一分量负折射,且在一定条件下可以同时全透射,从而实现大角度偏振分离。后者在一定条件下可实现入射波中的s分量和p分量某一分量全反射,另一分量全透射,从而实现偏振分离。最后,对从各向同性介质入射到这两种各向异性超常材料中的高斯光波的传输进行了模拟计算,结果表明这两种各向异性超常材料可以实现很好的偏振分离功能,有潜力成为新型的偏振分离元件。     

Focusing and phase compensation of paraxial beams by a left-handed material slab

On the basis of angular spectrum representation, a formalism describing paraxial beams propagating through an isotropic left-handed material (LHM) slab is presented. The treatment allows us to introduce the ideas of beam focusing and phase compensation by LHM slab. Because of the negative refractive index of LHM slab, the inverse Gouy phase shift and the negative Rayleigh length of paraxial Gaussian beam are proposed. It is shown that the phase difference caused by the Gouy phase shift in right-handed material (RHM) can be compensated by that caused by the inverse Gouy phase shift in LHM. If certain matching conditions are satisfied, the intensity and phase distributions at object plane can be completely reconstructed at the image plane.     

When optical microscopy meets all-optical analog computing: A brief review

As a revolutionary observation tool in life science, biomedical, and material science, optical microscopy allows imaging of samples with high spatial resolution and a wide field of view. However, conventional microscopy methods are limited to single imaging and cannot accomplish real-time image processing. The edge detection, image enhancement and phase visualization schemes have attracted great interest with the rapid development of optical analog computing. The two main physical mechanisms that enable optical analog computing originate from two geometric phases: the spin-redirection Rytov-Vlasimirskii-Berry (RVB) phase and the Pancharatnam-Berry (PB) phase. Here, we review the basic principles and recent research progress of the RVB phase and PB phase based optical differentiators. Then we focus on the innovative and emerging applications of optical analog computing in microscopic imaging. Optical analog computing is accelerating the transformation of information processing from classical imaging to quantum techniques. Its intersection with optical microscopy opens opportunities for the development of versatile and compact optical microscopy systems.     

冷源冷量对压缩/喷射制冷系统性能影响的实验研究

实验研究了喷射器的最优喷嘴距及在此条件下,冷凝器进水冷量对喷射器及双蒸发压缩/喷射制冷系统性能的影响,同时对双蒸发压缩/喷射制冷系统与蒸汽压缩制冷系统进行了对比研究。结果表明:喷射器引射系数随冷凝器进水冷量的增大而减小,喷射器升压比随冷凝器进水冷量的增大而增大;双蒸发压缩/喷射制冷系统COP_P随冷凝器进水冷量的增加先快速增加后缓慢减小,冷凝器进水冷量存在一个合理值,当冷凝器进水冷量控制在17.81 kW时,系统性能最好;高温蒸发器的制冷量约占系统总制冷量的88%,低温蒸发器的制冷量约占系统总制冷量的12%;在不同的冷凝器进水冷量下,双蒸发压缩/喷射制冷系统比蒸汽压缩制冷系统COP提高约36%左右。     

Zinc-catalyzed chemoselective reduction of tertiary and secondary amides to amines

General and convenient procedures for the catalytic hydrosilylation of secondary and tertiary amides under mild conditions have been developed. In the presence of inexpensive zinc catalysts, tertiary amides are easily reduced by applying monosilanes. Key to success for the reduction of the secondary amides is the use of zinc triflate and disilanes with dual Si-H moieties. The presented hydrosilylations proceed with excellent chemoselectivity in the presence of sensitive ester, nitro, azo, nitrile, olefins, and other functional groups, thus making the method attractive for organic synthesis.     

ABCD matrix formalism for propagation of Gaussian beam through left-handed material slab system

We apply a simple ABCD matrix formalism to investigate beam propagation in left-handed material (LHM) slab systems. Firstly, we derive the expressions for the matrix elements for a single LHM slab. Based on the ABCD matrix, we obtain the field distributions both inside and outside the LHM slab, and the conditions for focusing and phase compensation of the Gaussian beam. Secondly, the derived ABCD law is applied to analyze the propagation properties of Gaussian beams through various cascaded LHM slab systems. The corresponding focusing and phase compensation conditions of the Gaussian beam are also obtained. Our theoretic formalism may be applied as a compact and effective tool for the research of light beam propagation in complex LHM slab systems, since it avoids the complicated integral operation.